Cycloaddition Reactions of the Titanium Imide [Ti(NBu^t){MeC(2-C₅H₄N)(CH₂NSiMe₃)₂}(py)] with Bu^tCP and MeCN

Abstract

The diamidopyridine-supported titanium imide [Ti(NBuundergoes a [2+2] cycloaddition reaction with Bu t CP to form the mononuclear product [Ti{N(Bu t )PC(Bu t )}(L)] (2). In contrast, reaction of 1 with MeCN affords the binuclear derivative [Ti 2 {µ-η 2 -NC(Me)NBu t } 2 (L) 2 ] (3), which contains a doubly deprotonated N-tertbutylacetamidinate ligand. Compound 3 undergoes a quantitative cycloreversion reaction at elevated temperatures yielding MeCN and [Ti(NBu t )(L)] (4).

Alkaline Earth Metal Imido Complexes with Doubly Deprotonated Amidine and β‐Diketimine Ligands

“…Like the conversion of primary amines to RN 2– , the amidine RN=CR'‐NH 2 or β‐diketimine RN=C(Me)‐C(H)=C(Me)‐NH 2 could potentially be deprotonated twice. Complexes with the RN=C(Me)‐C(H)=C(Me)‐N 2– dianion have so far not been reported and examples of complexes with the RN=CR'–N 2– dianion are limited . Syntheses, structures, reactivities and the electronics of Ca and Sr complexes with these ligands are discussed.…”

A General and Facile One‐Step Synthesis of Imido–Titanium(IV) Complexes: Application to the Synthesis of Compounds Containing Functionalized or Chiral Imido Ligands and Bimetallic Diimido Architectures

“…in alkene metathesis [3] or olefin polymerization [1c,4-6] ), (2) reactions in which the M = NR linkage itself is involved in stoichiometric or catalytic transformations such as metathesis reactions (with imines, [7] nitro-and nitrosoarenes, [8] or oxo-imido exchange [9] ), C-H activation, [10] reactions with unsaturated C-C [11] or C-X bonds, [12] alkyne hydroaminations, [13,14] carboamination reactions, [15] and ring-opening reactions of strained heterocycles.…”

The Progression of Synthetic Strategies to Assemble Titanium Complexes Bearing the Terminal Imide Group

“…One clear illustration of such an approach has been reported by Mountford and co-workers using [{Cl 2 Ti=NSi(Me) 3 [113] Other examples of monomeric terminal imides prepared by breaking dimers or oligomers have been documented. [27,38,[113][114][115]…”

“…[3][4][5][6][7] For example, this type of functionality is responsible for fundamentally important reactions such as the intermolecular activation of aliphatic (including methane) [8,9] as well as aromatic C À H bonds. [7,[10][11][12][13] The ubiquitous imide group can also participate in other processes such as cycloaddition reactions with substrates like carbon dioxide, [14][15][16][17][18][19][20][21] carbon disulfide, [14-16, 19, 22] ke-tones, [16,22,23] alkenes (intra-and intermolecularly), [24,25] A C H T U N G T R E N N U N G alkynes, [22,[24][25][26] nitriles, [23,27] isonitriles, [16,28] imines, [16,23,29,30] carbodiimides, [4,16,[30][31][32] allenes, [4,24,33] allylic alcohols, [34] and carboxamides…”

“…For example, this type of functionality is responsible for fundamentally important reactions such as the intermolecular activation of aliphatic (including methane)8, 9 as well as aromatic CH bonds 7. 10–13 The ubiquitous imide group can also participate in other processes such as cycloaddition reactions with substrates like carbon dioxide,14–21 carbon disulfide,14–16, 19, 22 ketones,16, 22, 23 alkenes (intra‐ and intermolecularly),24, 25 alkynes,22, 24–26 nitriles,23, 27 isonitriles,16, 28 imines,16, 23, 29, 30 carbodiimides,4, 16, 30–32 allenes,4, 24, 33 allylic alcohols,34 and carboxamides35 along with several other polar reagents 4–7. Depending on the complex, incomplete or complete metathetical reactions can often take place (even catalytically) with these types of substrates, thus leading to Wittig‐like chemistry and extrusion of organic products in which the imide group has been swiftly incorporated.…”